Process for the treatment of rosins and metal salts produced thereby



Patented Nov. 29, 1938 UNITEDv STATES PROCESS FOR THE TREATMENT OF ROBINS A AND METAL SALTS PRODUCED THERE Edwin It. Littmann, Wilmington, Del., assignor to Hercules Powder Company, Wilmingt on, Del.,

a corporation of Delaware No Drawing. Original application June 12, 1986, Serial No. 84,877. Divided and this application September 9, 1936, Serial No. 100,043

16 Claims.

The objects of this invention are the treatment of rosins, rosin acids, and partially hydrogenated rosins so as to decrease their unsaturated characteristics, making metal salts of such products and the metal salts produced.

This treatment in accordance with this invention comprises essentially contacting rosin, a rosin acid, or other compound containing the hydrocarbon nucleus of a rosin acid with a catalyst of 11) the type hereinafter described, in a manner to exclude the possibility of reaction between the rosin or rosin derivative and any added material capable of reducing the unsaturation of the rosin acid nucleus. change in the chemical and physical properties of the rosin or rosin derivative takes place,'and the resultant product will be found to have a greatly decreased unsaturation. In many cases, the product will also be found to have a higher melting point and improved properties. These changes in the physical and chemical characteristics of the material are believed to be due to an intraand inter-molecular rearrangement of the hydrogen atoms occurring therein, with no change in the carbon skeleton.

The catalysts which may be used in effecting this change are those which catalyze the hydrogenation of unsaturated organic compounds, as, for example; nickel, copper chromite, platinum, palladium, etc. While both base and noblemetal hydrogenation catalysts are useful in producing this change or intraand inter-molecular rearrangement, a catalyst of noble metal supported on an inert carrier is particularly effective.

) Palladium in an amount within the range of about 1% to about 25% supported on an inert carrier, such as, for example, granular alumina or fibrous asbestos, is preferred.

A novel type of palladium catalyst, devised especially for the process in accordance with this invention, may be made as follows:

A solutioncontaining 1 part by weight of palladium chloride, 2 parts by weight of concentrated hydrochloric acid and 8 parts by weight As a result of such treatment a of water is adsorbed on 15 parts by weight of granular alumina. This mixture is then treated with 2 parts by weight of an approximately 37% formaldehyde solution, followed with approximately 15 parts by weight of an approximately sodium hydroxide solution, enough to make the solution slightly alkaline and precipitate the palladium black. After thorough agitation, the

mixture is filtered, washed with water, dilute acetic acid, and then again with water, until neutral. The product is then finally dried in an oven at 80 C. to 100 C. This catalyst is most eflicient in the treatment in accordance with this invention and its use is preferred.

Rosin is a mixture of isomeric rosin acids having the formula CmHzoCOOH, in which the group C19H29 has been shown to contain two double bonds and to possess an alkylated phenanthrene nucleus. It will be understood that when reference is made herein to a rosin acid, a carboxylic acid found in rosin and containing the group CZQHZQ, is meant. More than fifty different isomeric rosin acids have been reported in the literature. The best known of these acids are abietic acid, sapinic acid and d-pimaric acid. The relative proportions in which these and the other isomeric rosin acids occurin a given sample of rosin depends on the source of the rosin. Thus, wood rosin contains more abietic acid than any. of the other acids, while American gum rosin contains more saplnic-acid. French gum rosin contains more d-pimaric acid.

The hydrocarbon nucleus of each of these 150-.

meric acids is capable of reaction in accordance with this invention, and for the purposes of this invention theyare entirely equivalent. Thus, for

example, any of the various grades of American wood rosin, American gum rosin, French gum rosin, Portuguese gum rosin, Spanish gum rosin etc., may be treated to reduce their unsaturated characteristic. The several isomeric acids found in various types of rosin, foryexample, abietic acid, d-pimaric acid, sapinic acid, etc., may be separated and treated in purified form if desired. Likewise, compounds derived from rosin or the rosin acids without alteration of the CwHza nucleus are equivalent to the rosin or rosin acids for the purposes of this invention. Further, partially hydrogenated rosins and compounds containing a partially hydrogenated hydrocarbon nucleus of a-rosin acid are still further reduced in unsaturation when treated by the process in accordance with this invention and are. likewise equivalent to the unhydrogenated compounds from the standpoint of this invention. Such compounds are characterized by containing somewhere in their structure the hydrocarbon group CmHar containing one double bond, and are present in any hydrogenated rosin or rosin acid, less than 100% saturated with hydrogen, to an extent determined largely by the degree of saturation.

The class of compounds which may be treated in accordance with the process of this invention to decrease their unsaturation and improve their properties are characterized by containing somewhere in their structure an alkylated phenanthrene group containing two double bonds and having the formula CmHao or a partially hydrogenated phenanthrene group containing one double bond and having the formula Cl9H3L. No generic term has developed in the literature to cover this closely related group of compounds, so for convenience I will term them "rosinyl compounds. The term "rosinyl compound? will hereinafter be understood to include the abietyl compounds, the similar groups of compounds derived from rosin acids isomeric with abietic acid, partially hydrogenated abietyl compounds, and the similar partially hydrogenated compounds derived from rosin acids isomeric with abietic acid. This term is not intended to include rosins or compounds derived from rosins which. have been hydrogenated sufficiently to remove tion. Thus, for example, I may treat the monohydric and polyhydric alcohol esters of rosins, rosin acids, partially hydrogenated rosins, or partially hydrogenated rosin acids, such as, for example, their esters with methanol, ethanol, propanol, iso-propanol, butanol, iso-butanol, oleyl alcohol, lauryl alcohol, abietyl alcohol, hydroabietyl alcohol, furfuryl alcohol, tetra-hydrofurfuryl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, erytheritol, pentaerytherol, sorbitol, mannitol, mixtures thereof, phenol, etc. I may treat alcohols produced from rosins and rosin acids, partially hydrogenated rosins, or partially hydrogenated rosin. acids, by the reduction of the carboxyl groups of the rosin acids, such as, for example, abietyl alcohol, dihydroabietyl alcohol, sapinyl alcohol, dihydrosapinyl alcohol, pimaryl alcohol, dihydropimaryl alcohol, etc. Again, I may treat ethers formed by the etherification of the alcohols derived from rosins, rosin acids, partially hydrogenated rosins, and partially hydrogenated rosin acids with aliphatic aromatic, or hydroaromatic alcohols, such as, for example, 'abietyl methyl ether, abietyl ethyl ether, abietyl butyl ether, abietyl phenyl ether, abietyl bornyl ether, abietyl terpinyl ether,

pimaryl methyl ether, pimaryl ethyl ether, pimaryl propyl ether, pimaryl phenyl ether, pimaryl bornyl ether, pimaryl terpinyl ether, sapinyl methyl ether, sapinyl ethyl ether, sapinyl propyl ether, sapinyl butyl ether, sapinyl phenyl ether, sapinyl bornyl ether, sapinyl terpinyl ether, etc. Likewise, I may treat hydrocarbons produced by the decarboxylation of rosins, rosin acids, partially hydrogenated rosins, partially hydrogenated rosin acids, etc., such as. for example, those produced by the treatment of rosins, rosin acids, partially hydrogenated rosins and partially hydrogenated rosin acids with a catalyst, as, p-toluene sulphonic acid, at an elevated temperature, according to the process disclosed in U. S. Patent 1,975,211 to Alan C. Johnston, or by treatment with fullers earth at an elevated temperature.

Compounds which contain in their structure a rosin acid nucleus or partially hydrogenated rosin acid nucleus which has undergone the intraand inter-molecular rearrangement produced by the process in accordance with this invention, will hereinafter be referred to as Hyex compounds. The catalytic reaction by which the unsaturation of the rosin acid nucleus or the partially hydrogenated rosin acid nucleus is reduced will be termed the Hyex reaction".

In carrying out the process in accordance with this invention, the rosinyl compound will be brought into contact with a hydrogenation catalyst, preferably at an elevated temperature in order that a practical reaction rate may be obtained; however, the use of an elevated temperature is not necessary forthe accomplishment of the desired result. The optimum temperature range for most satisfactory results is from about 150 C. to about 250 0., and a tem-- perature of about 220 C. to about 250 C. is preferred. Pressure has little or no effect on the reaction, which may be carried out in vacuo or at superatmospheric pressure if desired. Since atmospheric pressure is most convenient from an apparatus standpoint, such will usually be used.

As thorough contact between catalyst and rosin or rosin acid can best be obtained when the rosinyl compound or partially hydrogenated rosinyl compound is in liquid or vapor phase, the rosinyl compound or partially hydrogenated rosinyl compound will preferably be heated to render it sufflciently fluid for desired contact with the catalyst. While, under certain circumstances it is desirable to carry out the reaction in the vapor phase, ordinarily I prefer to carry it out with a liquid phase. The rosinyl compound or the partially hydrogenated rosinyl compound may be in the molten condition or may, if desired, be dissolved in a suitable inert, non-reactive solvent, and the solution so formed treated with a hydrogenation catalyst. Any solvent for the compound treated which is not a poison to a hydrogenation catalyst and which does not contain catalyst poisons as impurities and which does not enter into the Hyex reaction is suitable for this purpose. Thus, for example, aliphatic hydrocarbons, the various petroleum fractions, monocyclic aromatic hydrocarbons, hydrogenated aromatic hydrocarbons, etc., are suitable for the purpose. The aliphatic hydrocarbons and the various petroleum fractions are particularly useful.

In accordance with this invention it is essential that the treatment of the rosinyl compound aisaiss be carriedoutinsuchamannerthatnor'eaction can occur between the compound being treated and any added material capable of reducing its unsaturation under the conditions of reaction. In other words, any material which, under the conditions of treatment, will react with the rosinyl compound to reduce its unsaturation must be excluded. No added hydrogen -is present during the treatment. However, inert substances and substances capable of reaction with the compound which do not reduce its unsaturation, may be present. Thus, inert solvents, inert gases, etc. may be present. While the treatment may be carried out in the presence air, it, is preferable to treat the rosinyl compound or the partially hydrogenated rosinyl compound in an atmosphere 01 a more inert gas, as, for example, carbon dioxide, nitrogen, etc.

The treatment in accordance withthis invention may be carried outsimultaneously with other reactions, which do not involve a change in the unsaturated characteristic of the rosin nucleus. Thus, rosin or a rosin acid may be treated with a hydrogenation catalyst to produce an intraand inter-molecular rearrangement of the nucleus and, for example, simultaneously esterifled with an alcohol, to produce a rosin ester of reduced unsaturation.

Contact between the rosinyl compound or the part ally hydrogenated rosinyl compound and the catalyst should be maintained for from a few seconds to 5 hours or more, depending upon the temperature and upon the amount and activity of the catalyst employed. Upon the completion of the treatment, the resultant product may be easily separated from the catalyst by filtration. The product secured after the removal of the catalyst, if volatile, may if desired, be distilled under reduced pressure and separated into two or more fractions. Where alhigh melting point product is desired, such may be secured by the removal of the low-boiling-fraction from the catalytically-treated material.

The product, in accordance with this invention, may be produced by one or more of the three alternate embodiments of the method in accordance with this invention. By the first of these alternate embodiments the corresponding rosinyl compound may be treated, either alone or in solution, with a suitable catalyst to produce the Hyex reaction, as described hereinbefore. This embodiment will be most advantageous for the treatment of rosin compounds which are free from impurities which will poison the catalyst, or which are not of such nature that they act as catalyst poisons. Thus, rosin may be contacted with a catalyst to produce a Hyex rosin, or a rosin ester may be passed over a catalyst to produce Hyex rosin ester.

By a second embodiment of the method in accordance with this invention a rosinyl compound may be treated with a suitable catalyst to produce the Hyex reaction, and simultaneously reacted, either alone or in the presence of a solvent, with some other material which is incapable of affecting the unsaturation of the rosin acid or partially hydrogenated rosin acid nucleus or of poisoning the hydrogenation catalyst. Thus, a mixtureof wood rosin and methanol may be treated with a suitable catalyst at an elevated temperature and pressure to produce a Hyex methyl abietate, which is identical in properties with the product secured by subjecting methyl abietate to the Hyex reaction.

- may be treated, either alone or in solution, with a suitable catalyst to produce the-Hyex reaction and the product so formed reacted with another material to produce the desired product. Thus,

for example, any oi the diflerent rosins may be contacted with a suitable catalyst, as hereinbeiore described, to produce a Hyex rosin, and then estei'ined by reaction, with an alcohol to produce the Hyex rosin ester and the Hyex rosin ester so produced will be identical in properties with the Hyex rosin ester produced according to the first or second embodiments of my invention.

A wide variety 'oi Hyex compounds may be prepared by this embodiment of my invention. Thus, any one of the rosins. rosin acids, or partially hydrogenated rosins mentioned above may be subjected to the Hyex reaction, and then decarboxylated as, for example, by heating in contact with fullers earth orasulphonic acid catalyst to produce a Hyex rosin oil. A rosin or rosin ester may be subjected to Hyex treatment and then reduced to the corresponding alcohol, as for example, by hydrogenation oi the acid, or reduction of the ester with sodium and alcohol. The alcohol so produced may then be etherifled with another alcohol, such as, for example, one of the aliphatic, aromatic, or hydroaromatic alcohols mentioned hereinbei'ore. Alternately, a rosin acid may be reduced to the corresponding alcohol, as for example, by catalytic treatment with hydrogen and the product subjected to the Hyex reaction and then etherifled.

This third embodiment of my invention is particularly useful for the production oi Hyex compounds which cannot be easily produced by the first or second alternative methods, due to the corresponding rosinyl compound or partially bydrogenated rosinyl compound being of a nature such that it acts as a poison to'the catalyst in the Hyex reaction. Thus, for example, many of the metal salts of rosin acids or partially hydrogenated rosin acids have a tendency to poison the catalyst or to contain catalyst poisons unless proper precautionary measures are taken and, hence, cause difllculty in the Hyex reaction. Hyex rosin salts, however, may be readily prepared by subjecting a rosin acid or a partially hydrogenated rosin acid to the Hyex reaction and then forming the salt of the Hyex rosin acid produced. Thus, any one of the rosins, rosin acids, or partially hydrogenated rosins mentioned above may be subjected to the Hyex reaction and then reacted with a metal hydroxide or other metal compound, capable of forming a metal salt with the Hyex rosin acid. Thus, the Hyex rosin acid may be reacted with an alkali metal hydroxide, for example, sodium or potassium hydroxide, to produce the corresponding alkali metal salt of the Hyex rmin with a heavy metal oxide or hyboxylic acid, ester, alcohol, ether, hydrocarbon, 7

metal salt, etc. These compounds will be found to resemble, in general physical appearance, the compounds which have not been treated by the methodlin accordance with this invention, although frequently they are lighter in color and have a higher melting point than the corresponding untreated product. Chemically the treated and untreated compounds are identical withrespect to the functional group, but different in regard to their chemical unsaturatiori.

Due to the substantially saturated character of the products prepared in accordance with this invention, their use will be found to be highly advantageous in many products in which untreated rosinyl compounds are now used. Thus, Hyex rosin; Hyex rosin acids. Hyex rosin ethers, etc. will be found advantageous for use in paints, varnishes and lacquers, in place of the correspending rosinyl compounds which have been used before. The Hyex rosin oils, because of their stability to oxidation, will be found useful as thread lubricants in spinning operations, as high boiling solvents. for gums and resins, and as ingredients in greases. The alkali metal salts of the Hyex rosins are useful as paper size and soaps, and are advantageous in this use due to their resistance to chemical oxidation and as intermediates for additional syntheses. The heavy metal salts of Hyex rosin, such as, for example, those containing manganese, cobalt, zinc, lead, etc., are particularly useful as driers in'paints and varnishes. since solutions containing such driers remain bright and of constant drying strength on aging.

The carboxylic acids included within the scope of this invention are the isomeric rosin acids, or commercial mixtures thereof in the various types of rosins, mentioned hereinbefore, which have been subjected to the Hyex treatment. The esters, in accordance with this invention, are compounds having the following formula: R--COO--A in which R is a hydrocarbon nucleus of one of the isomeric rosin acids, which has been subjected to the Hyex treatment either before, during, or after the esteriflcation reaction and A is a group derived from an alcohol. The ethers, in accordance with this invention, are compounds having the following formula: RCH2--OA in which the ,R and A have the same meaning as in the formula given for the esters. The hydrocarbons, in accordance with this invention, are the hydrocarbon nuclei of the isomeric rosin acids which have been subjected to the Hyex treatment and from which the carboxyl group has been removed. Such Hyex rosinyl hydrocarbons may be produced by subjecting rosin or a rosin acid to the Hyex treatment and then treating the resulting Hyex rosin or Hyex rosin acid to remove the carboxyl group. Alternately the rosin or rosin acid may be decarboxylated, by treatment with a suifonic acid catalyst or any other reagent known to produce the decarboxylation of rosin, and the resulting hydrocarbon then subjected to the I-Lvex treatment. The salts, in accordance with this invention, are metal salts of a Hyex rosin or Hyex rosin acid. Such salts will desirably be produced by subjecting the rosin or rosin acid to the Hyex treatment and then forming the salt by reaction with a suitable metal compound, such as, for example, the metal hydroxide. Alternately, but less desirable, the rosin or rosin acid may be treated with a suitable metal compound to form the .salt,

and ime salt then subjected to the Bye: treatmen The following table shows comparative values of various chemical constants for rosin which has been subjected to the Hyex reaction together with those of the corresponding untreated rosin.

, Tun I "I" WM rosin (beiore H x "1" wood rosin treatment) 1' Thiocyanste number.... 90-06 10-14 Melting point (drop) -86 O. SIP- 0. Color- Very slight bleaching figo duced by reacgsponiflcstion Ilitll1mbQ(l'...- 168-11: 167-171 xygen adsoi on rcent oi to edsorwed 1 by two double bonds).

Tssu: II

Abictic acid (before treat- Hyex abietic acid ment) Thiocyanate number 90-93 Melting Boint 160 O. IBM-16 Color (w an melted) Pale straw Practically colorless Oxygen adsorption r- 65 None cent of tots adsor by two double bonds).

Here, as in the case of 1" rosin, the lowered thiocyanate number and oxygen adsorption demonstrate the saturated character of the treated abietic acid.

The examples which follow illustrate the procass and products in accordance with this inven- Exsuru: I

Preparation of Hues: rosins and Huea: rosin acids Samples of French gum rosin, dihydroabletic acid (50% saturation), recrystallized dihydroabietlc acid (50% saturation), FF" grade wood rosin, and G grade American gum rosin, respectively, were contacted with a catalyst of palladium supported on alumina, which was prepared as described hereinbefore, for a period of one hour at a temperature of 230 C., under conditions such that no compound capable of reducing unsaturation came in contact with the rosin treated. The physical and chemical characteristics of each of these rosins were altered by this treatment, as shown by the comparison of the properties or the treated and untreated samples given, in the following table:

of Hyex wood rosin, suitable for use as a paper Tasu III Analyses of Hyex resins Thiooyanate Melting int I number (drorg q Rosin treated v a Un- Treat- Un- Treat-- Unmmo od treated ed. treated French gumrosln 100 24 02 0 as" o. 15.0 simulate. Dihzdrosbietio acid(50% 40 a or 21.3 63.6.

saurstion). Dihydroabletio acid (re- 21 4 so 43.2 51.1.

0i 5 "F "wood rosin 99 80 86 83 "G" American gum rosin. 94 8 90 95 These data. demonstrate that the treatment of each or the rosins and rosin acids listed, by the process in accordance with this invention, makes substantial reduction in their unsaturation, as

shown by the decrease in the thiocyanate number. and substantially increases the melting point.

I Exuugn: II

Preparation of Hues: wood rosin in solution A mixture or 25 parts by weight of I wood rosin, 10 parts by weight of the palladium catalyst supported on granular alumina described hereinbefore, and. 25 parts by weight of decane was placed in a bomb and heated to a temperature of 235 C. and a pressure of '75 lbs. per sq. in. for one hour. At the end of this period, the product was filtered and the treated rosin recovered from the decane solution by evaporating the decane under atmospheric and finally under reduced pressure. Comparative analyses of this product and of the original 1 wood rosin are given in Table IV.

Tasnn IV 1" wood rosin Treated 1" (untreated) wood rosin Thiocyanato value 93 16 Acid number 169 159 The data given in the above table demonstrate that the treatment of a solution of 1 wood rosin in decane, in accordance with this invention, produces a marked decrease in the unsaturation oi the "1 wood rosin, as measured by the thiocyanate value, with a relatively unimportant decrease in acidity, as measured by the acid number.

Exaurns III Preparation of the sodium salt of Hyex wood rosin Exmu IV Preparation of the zincsalt of Hyex wood rosin A solution of the sodium salt 0! Hyexwood rosin prepared as described in Example 111 was poured with stirring into a cool aqueous solution of the equivalent quantity 0! zinc sulfate. The precipitated zinc salt was filtered off, washed free of electrolytes and dried in a vacuum oven at 55 C. The product was the zinc salt of Hyex wood rosin, which is suitable for use as a dryer in paints and varnishes.

Exhurrs V Preparation of the lead salt of Hyex wood rosin The lead salt of Hyex wood rosin was prepared by the same procedure described in Example IV, except that an aqueous solution of lead acetate clarified by the addition of a small amount of acetic acid was used instead of an aqueous solution of zinc sulfate. The product was the lead salt of Hyex wood rosin which is suitable for use as a dryer in paints and varnishes.

Exmru: VI

Preparation of the calcium salt of Hues: wood rosin EXAMPLE VII Preparation of the calcium salt of Hyex American gum rosin The procedure given in Example VI was duplicated, using the Hyex American gum rosin described in Table III, instead of Hyex wood rosin.

EXAMPLE VIII Preparation of the lead salt of Hyex American gum rosin To g. of the Hyex American gum rosin described in Table III was added 26.5 g. of lead oxide (PhD) in small proportions and with constant stirring. After the addition of the lead oxide and the slowing up of the initial violent neutralization the temperature was raised to 270 C. and the product filtered through cloth. If

neutralization takes place with difficulty indollowing ,this procedure, the reaction may be catalyzed by the addition of a small amount of calcium acetate.

Exmu 1X Preparation 0/ the manganese salt 0/ Hues: French gum rosin showed no discoloration after standing in air for several days. This powder was the manganese salt of Hyex French gum resin.

The fact that the changes in a rosinyl compound caused by the. Hyex treatment, in accordance with this invention, occur solely within the hydrocarbon nucleus derived from a rosin acid in the rosinyl compound treated, and; that identical compounds can be produced by following the different embodiments of the method in accordance with this invention, is strikingly demonstrated by the following experiment:

Abietic acid was given the Hyex treatment in accordance with this invention to produce a Hyex abietic acid having the properties shown by the analyses given in Table 11, above. This product was then esterified with methyl alcohol and the ester nitrated.' The resultant crystalline nitrate melted at 185 C. Pure methyl abietate, made from untreated abietic acid was then given the Hyex treatment by the method in accordance with this invention as shown in Example I, above, and subsequently nitrated. This crystalline nitrate also melted at 185 C., and a mixture of this nitrate and the nitrate produced as described above melted sharply at 185 C. The two nitrates are thus proved to be chemically identical, which proves that the Hyex treatment in accordance with this invention aflects only the hydrocarbon nucleus of the rosinyl compound.

It will be understood that the details and examples hereinbefore set forth are illustrative only, and that the invention as herein broadly described and claimed is in no way limited thereby.

It will be understood that the term "unsaturation is used in this specification and in the appended claims to refer to the unsatisfied carbon valences of the type represented by a double bond in unsaturated aliphatic compounds and conveniently measured by the thiocyanate value.

This application is a division of my application for United States Letters Patent, Serial No. 84,877, filed June 12, 1936, which is in turn a continuation-in-part of my application for United States Letters Patent, Serial No. 6,403, flied February 13, 1935.

What I claim and desire to protect by Letters Patent is:

1. A compound of the formula R-COO-M in which R is the hydrocarbon nucleus of an acid of the group consisting of rosin, rosin acids, par tially hydrogenated rosin, and partially hydrogenated rosin acids, which has, in the absence of any added substance capable of reducing the unsaturation of the hydrocarbon nucleus under the conditions of treatment, been treated with a disseminated hydrogenation catalyst which is subsequently removed from the compound,- and M is a a metal, the said compound being characterized by the fact that it has a lesser degree of unsaturation than that of a similar compound in which R'is untreated.

2. A compound of the formula RfCQO-M in which R is the hydrocarbon nucleus of an acid of the group consisting of rosin, rosin acids, partially hydrogenated resin, and partially hydrogenated rosin acids, which has, in the absence of any added substances capable of reducing the unsaturation of the hydrocarbon nucleus under the conditions of treatment, been treated with a disseminated hydrogenation catalyst which is subsequently removedfrom the compound, and M is an alkali metal, the said compound being characterized by the fact that it has a lesser degree of unsaturation than that of a similar compound in which R is untreated.

3. A compound of the formula RCOOM in which R is the hydrocarbon nucleus of an acid of the group consisting of rosin. rosin acids, partially hydrogenated rosin, and partially hydrogenated rosin acids, which has, in the absence of any added substance capable of reducing the unsaturation of the hydrocarbon nucleus under the conditions of treatment, been treated with a disseminated hydrogenation catalyst which is subsequently removed from the compound, and M is a heavy metal, the said compound being characterized by the fact that it has a lesser deree of unsaturation than that of a similar compound in which R is untreated. I

4. A compound of the formula HOD-M in which R is the hydrocarbon nucleus of an acid of the group consisting of rosin, rosin acids, partially hydrogenated rosin, and partially hydrogenated rosin acids, which has, in the absence of any added substance capable of reducing the unsaturation of the hydrocarbon nucleus under the conditions of treatment, been treated with a disseminated hydrogenation catalyst which is subsequently removed from the compound, and M is a heavy metal selected from the group consisting of manganese, cobalt, zinc, and lead, the said compound being characterized by the fact that it has a lesser degree of unsaturation than that of a similar compound in which R is untreated.

5. A compound of the formula R-COOM in which R is the hydrocarbon nucleus of an acid of the group consisting of rosin, rosin acids, partially hydrogenated rosin, and partially hydrogenated rosin acids, which has, in the absence of any added substance capable of reducing the unsaturation of the hydrocarbon nucleus under the conditions of treatment, been treated with a disseminated hydrogenation catalyst which is subsequently removed from the compound, and M is sodium, the said compound being characterized by the fact that it has a lesser degree of unsaturation than that of a similar compound in which R is untreated.

6. A compound of the formula R-COO-M in which R is the hydrocarbon nucleus of an acid of the group consisting of rosin, rosin acids, partially hydrogenated rosin, and partially hydrogenated rosin acids, which has been treated with a hydrogenation catalyst in the absence of any added substance capable of reducing the unsaturation of the hydrocarbon nucleus under the conditions of treatment, and M is cobalt, the said compound being characterized by the fact that it has a lesser degree of unsaturation than that of a similar compound in which R. is untreated.

'7. A compound of the formula RA-COO-M in which R is the hydrocarbon nucleus of an acid of the group consisting of rosin, rosin acids, partially hydrogenated rosin, and partially hydrogenated rosin acids, whlch has, in the absence of any added substance capable of reducing the unsaturation of the hydrocarbon nucleus under the conditions of treatment, been treated with a disseminated hydrogenation catalyst which is subsequently removed from the compound, and M is lead, the said compound being characterized by the fact that it has a lesser degree ofunsaturation than that of a similar compound in which R is untreated.

8. The method of producing a salt of a resin acid which includes contacting an acid material from the group consisting of rosins, rosin acids, partially hydrogenated rosins, and partially hydrogenated rosin acids with a disseminated hydrogenation catalyst in the absence of added substances capable of reducing the unsaturation oi the material, separating the resulting acid material from the hydrogenation catalyst and then reacting the resulting acid material with a metal compound to form a salt.

9. The method of producing a salt of a resin acid which includes heating an acid material from the group consisting of rosins, rosin acids, partially hydrogenated rosins, and partially hydrogenated rosin acids with a disseminated hydrogenation catalyst in the absence of added substances capable of reducing the unsaturation of the material, separating the resulting acid material from the hydrogenation catalyst and then reacting the resulting acid material with a metal compound to form a salt.

10. The method of producing a salt of a resin acid' which includes heating an acid material from the group consisting of rosins, rosin acids, partially hydrogenated rosins, and partially hydrogenated rosin acids with a disseminated hydrogenation catalyst at a temperature within the range of about 150 C. to about 250 C. in the absence of added substances capable of reducing the unsaturation of the material, separating the resulting acid material from the hydrogenation cat-,

alyst and then reacting the resulting acid material with a metal compound to form a salt.

11. The method of producing a salt of a resin acid which includes contacting an acid material from the group consisting of rosins, rosin acids, partially hydrogenated rosins, and partially hydrogenated rosin acids with a noble metal hydrogenation catalyst in the absence of added substances capable of reducing the unsaturation of the material, and reacting the resulting acid material with a metal compound to form a salt.

12. The method of producing a salt of a resin acid which includes contacting an acid material from the group consisting of rosins, rosin acids, partially hydrogenated'rosi'ns, and partially hydrogenated rosin acids with a disseminated base metal hydrogenation catalyst in the absence of added substances capable of reducing the unsaturation of the material, separating the resulting acid material from the hydrogenation catalyst and then reacting the resulting acid material with a metal compound to form a salt.

13. The method of producing a salt of a resin acid which includes contacting an acid material from the group consisting of rosins, rosin acids.

partially hydrogenated rosins, and partially hy-' drogenated rosin acids with a palladium hydrogenation catalyst in the absence of added substances capable of reducing the unsaturation of the material, and reacting the resulting acid .material with a metal compound to form a salt.

14. The method of producing a salt of a resin acid which includes contacting an acid material from the group consisting of rosins, rosin acids, partially hydrogenated rosins, and partially hydrogenated rosin acids with a catalyst comprising palladium black supported on granular alumina -in the absence of added substances, capable of reducing the unsaturation of the material, and reacting the resulting acid material with a metal compound to form a salt.

15. The method of producng a salt of a resin acid which includes heating an acid material from the group consisting of rosins, rosin acids, partially hydrogenated rosins, and partially hydrogenated rosin acids with a catalyst compris-v ing palladium black supported on alumina at a temperature within the range of about C. to about 250 C. in the absence of added substances capable of reducing the unsaturation of the material, and reacting the resulting acid material with a metal compound to form a salt.

16. The method of producing a salt of a resin acid which includes contacting an acid material from the group consisting of rosins, rosin acids, partially hydrogenated rosins, and partially hydrogenated rosin acids with a disseminated hydrogenation catalyst in theabsence of added substances capable of reducing the unsaturation of the material, separating the resulting acid materialfrom the hydrogenation catalyst and then neutralizing theacidity oijthe material with a basic compound. f

R. LI'I'I'MANN. 

